Monoazo and diazo colorants from aminoalkylanilines and bis(aminoalkyl)anilines

ABSTRACT

Water-insoluble azo dyestuffs of the formula ##STR1## AND WATER-SOLUBLE ACID ADDITION SALTS THEREOF USEFUL FOR COLORING NATURAL FIBERS, SYNTHETIC FIBER-FORMING MATERIAL AND CELLULOSIC MATERIALS AS WELL AS IN THE MANUFACTURE OF PAPER, VARNISHES, INKS, COATINGS AND PLASTICS IN WHICH A represents an azoic coupling radical derived from a coupling component selected from the group consisting of arylides of hydroxysubstituted carbocyclic aromatic carboxylic acids, 1-aryl-5-hydroxypyrazoles, 6-amino-1-naphthol-3-sulfonic acid, and compounds having an enolizable ketomethylene group of the formula ##STR2## R is hydrogen, lower-alkyl, lower-alkoxy or halogen; R 2  is hydrogen, lower-alkyl, lower-alkoxy, halogen, aminomethyl or 2-aminoethyl with the proviso that A is other than β-naphthol when R 2  is aminomethyl or 2-aminoethyl; R 1  and R 3  are the same or different and are each hydrogen, lower-alkyl, lower-alkoxy, halogen or aminomethyl with the proviso that at least one of R 1  and R 3  is aminomethyl when R 2  is other than aminomethyl or 2-aminoethyl; and n represents an integer whose value is 1 or 2 and corresponds to the number of azo linkages, which dyestuffs are obtained by coupling a diazotized amine of the formula ##STR3## in which R, R 1 , R 2  and R 3  are as defined above with said coupling component.

This application is a division of my now abandoned application Ser. No.641,566, filed on Dec. 17, 1975, which in turn is a continuation-in-partof my now abandoned application Ser. No. 548,015, filed Feb. 7, 1975.

BACKGROUND OF THE INVENTION

(a) Field of the Invention

This invention relates to the field of chemistry and more particularly,to novel basic azo dyestuffs and to the acid addition salt formsthereof.

(B) Description of the Prior Art

Lacey U.S. Pat. No. 2,761,868 (patented Sept. 4, 1956) discloses greenand blue basic dyestuffs of the phthalocyanine series bearing from oneto eight aminomethyl groups.

German Pat. No. 82,626 (granted July 1, 1895) discloses basic azodyestuffs obtained by diazotization of p-aminobenzylamine and couplingof the diazonium compound with beta-naphthol and resorcinol.

SUMMARY OF THE INVENTION

In its composition of matter aspect, the invention relates to certainwater-insoluble azo dyestuffs of the formula ##STR4## useful forcoloring natural fibers, synthetic fiber-forming material and cellulosicmaterials as well as in the manufacture of paper, varnishes, inks,coatings and plastics and to the acid addition salt forms of thedyestuff.

In its process aspect, the invention relates to a process for preparingthe water-insoluble azo dyestuffs of Formula I which comprisesdiazotizing an appropriate 2-R-3-R¹ -4-R² -5-R³ -aniline and couplingthe resulting diazonium salt with a coupling component from which theazoic coupling radical represented by A in Formula I is derived.

DETAILED DESCRIPTION INCLUSIVE OF THE PREFERRED EMBODIMENTS

More specifically, this invention, in its composition of matter aspect,resides in the novel water-insoluble azo dyestuffs and in thewater-soluble acid-addition salt forms thereof, of the formula ##STR5##wherein: n is an integer whose value is one or two; R is hydrogen,lower-alkyl, lower-alkoxy or halogen; R² is hydrogen, lower-alkyl,lower-alkoxy, halogen, aminomethyl or 2-aminoethyl with the proviso thatA is other than β-naphthol when R² is aminomethyl or 2-aminoethyl; R¹and R³ are the same or different and are each hydrogen, lower-alkyl,lower-alkoxy, halogen or aminomethyl with the proviso that at least oneof R¹ and R³ is aminomethyl when R² is other than aminomethyl or2-aminoethyl; A is an azoic coupling radical which when n is one isselected from the class having the formulas ##STR6## and, when n is two,is selected from the class having the formulas ##STR7## in which Q, Q¹and Q² are the same or different and are each hydrogen, lower-alkyl,lower-alkoxy, nitro or halogen; and Q³ is hydrogen, lower-alkyl,lower-alkoxy or halogen.

In the first particular embodiment in accordance with its composition ofmatter aspect, the invention sought to be patented resides in the novelmonoazo chemical compounds of Formula I wherein n is one and A is anazoic coupling radical having the formula ##STR8## in which Q, Q¹ and Q²each have the same respective meanings indicated in relation to FormulaI. Preferred compounds within the ambit of this particular embodimentare of the formula ##STR9## wherein Q, Q¹, Q², R, R¹, R² and R³ eachhave the same respective meanings given in relation to Formula I.

In a second particular embodiment in accordance with its composition ofmatter aspect, the invention sought to be patented resides in the novelmonoazo chemical compounds having the formula ##STR10## in which R, R¹,R² and R³ each have the same respective meanings given in relation toFormula I.

In a third particular embodiment in accordance with its composition ofmatter aspect, the invention sought to be patented resides in the novelmonoazo chemical compounds of the formula ##STR11## in which R, R¹, R²and R³ each have the same respective meanings given in relation toFormula I.

In a fourth particular embodiment in accordance with its composition ofmatter aspect, the invention sought to be patented resides in the novelmonoazo chemical compounds having the formula ##STR12## in which Q, Q¹,Q₂, R, R¹, R² and R³ each have the same respective meanings given inrelation to Formula I.

In a fifth particular embodiment in accordance with its composition ofmatter aspect, the invention sought to be patented resides in the noveldisazo chemical compounds of the formula ##STR13## in which Q³, R, R¹,R² and R³ each have the same respective meanings given above in relationto Formula I.

In a sixth particular embodiment in accordance with its composition ofmatter aspect, the invention sought to be patented resides in the noveldisazo chemical compounds having the formula ##STR14## in which R, R¹,R² and R³ each have the same respective meanings given in Formula I.

In its process aspect, the invention sought to be patented resides inthe process which comprises diazotizing an amine of the formula##STR15## and coupling approximately n molecular proportions of thediazonium salt with one molecular proportion of a coupling componentfrom which the azoic coupling radical A is derived to yield an azodyestuff having the structure shown in Formula I and in which A, n, R,R¹, R² and R³ have the same significance as in Formula I.

A particular embodiment in accordance with the process aspect of theinvention resides in the process which comprises diazotizing an amine ofthe formula ##STR16## and coupling approximately one molecularproportion of the coupling component of the formula ##STR17## to yieldan azo dyestuff having the structure shown in Formula II and in which Q,Q¹, Q², R, R¹, R² and R³ have the same respective meanings indicated inrelation to Formula II.

Another particular embodiment in accordance with the process aspect ofthe invention resides in the process which comprises diazotizing anamine of the formula ##STR18## and coupling approximately two molecularproportions of the diazonium salt with one molecular proportion of thecoupling component of the formula ##STR19## to yield an azo dyestuffhaving the structure shown in Formula VI and in which Q³, R, R¹, R² andR³ have the same respective meanings indicated in relation to FormulaVI.

As used throughout, the term "halogen" includes bromine, chlorine,fluorine and iodine.

As used herein, the term "lower-alkyl" is a saturated straight- orbranched-chain aliphatic radical of from one to three carbon atomsrepresented, for example, by methyl, ethyl, propyl and isopropyl.

Similarly, the term "lower-alkoxy" includes straight- or branched-chainaliphatic groups attached to the oxygen atom. Included, for example, inthis term are methoxy, ethoxy, propoxy and isopropoxy.

The new dyestuffs of this invention are the water-insoluble basic azocompounds obtained by coupling the appropriate diazotized monoaminomethylated-, mono-aminoethylated- or bis(aminomethylated)-anilinewith the appropriate coupling component, and the water-solubleacid-addition salt forms of said basic azo compounds.

The azoic coupling radicals represented by A are derived from couplingcomponents which are generally known in the dyestuff art. The couplingcomponents used herein are essentially of two types. One type iscomprised of carbocyclic or heterocyclic aromatic compounds bearing ahydroxyl group which compounds are capable of coupling in a positionvicinal to said hydroxyl group, for example, the arylamides of2-hydroxy-3-naphthoic acid and 1-aryl-3-methyl-5-hydroxypyrazoles.

The second type of coupling component useful in this invention comprisescompounds containing in an open carbon chain an enolizable ketomethylenegroup of the formula ##STR20## for example, the arylamides ofacetoacetic acid. Many of the coupling components useful in thisinvention are designated in the prior art by a Naphtol AS designation.Where applicable, this designation will be used together with thechemical name.

The novel basic azo dyestuffs of the invention provide shades rangingfrom yellow through orange and red to blue-scarlet which in thefree-base form have valuable properties as water-insoluble pigments, andin the acid-addition salt form as water-soluble direct dyes, useful inthe dyeing art for coloring natural fibers, synthetic fiber-formingmaterials and cellulosic materials such as threads, sheets, fibers,filaments, textile fabrics and the like, as well as in the manufactureof paper, vanishes, inks, coatings and plastics.

The water-insoluble pigments and the water-soluble acid-addition saltsthereof of this invention are characterized by good light-fastness. Thepigments in the form of their water-soluble acid-addition salt form areuseful as dyes for dyeing operations, and in the water-insolublefree-base form as pigments for printing operations on woven andnon-woven substrates made from natural fibers, such as wool, celluloseor linen, those made from semi-synthetic fibers, such as regeneratedcellulose as represented by rayon or viscose, or those made fromsynthetic fibers, such as polyaddition, polycondensation orpolymerization compounds. Such dyeings or printings can be carried outin accordance with the usual dyeing and printing processes. Thewater-insoluble pigments can also be added to spinning solutions priorto polycondensation or polymerization.

The water-insoluble basic azo pigments of this invention are alsosuitable for surface coloring or printing paper and cardboard as well asfor coloring paper pulps. Moreover, they are useful for incorporationinto lacquers and films of various constitution, for example, those madefrom cellulose acetate, cellulose propionate, polyvinyl chloride,polyethylene, polypropylene, polyamides, polyesters of alkyd resins. Inaddition the subject compounds are suitable for coloring natural orsynthetic resins, for example, acrylic resins, epoxy resins, polyesterresins, vinyl resins, polystyrene resins, or alkyd resins.

The basic azo dyestuffs of this invention are readily converted towater-soluble dyes by treatment with an aqueous solution containing astoichiometric amount of an inorganic mineral acid selected from thegroup consisting of hydrochloric, nitric and phosphoric acids or with anorganic acid selected from the group consisting of acetic, glycolic,formic, lactic and methanesulfonic acids. The acid-addition salt formscan be isolated from the aqueous solution in which they are formed bytechniques well known in the art, for example, by salting out,precipitation or concentration by evaporation. However, thewater-soluble dyes thus formed are readily utilized in the form ofaqueous solutions for many of their applications, particularly fordyeing cellulose. Accordingly, it is particularly preferred to retainthe dyes in a concentrated aqueous solution of the type regularlyemployed in the paper industry for dyeing paper products.

The water-soluble acid-addition salt form of the subject basic azodyestuffs are especially valuable dyes for imparting various shades of astable red, scarlet, orange or yellow color to cotton and to paper, bothsized and unsized. For use in the paper trade, the dyes of thisinvention have several outstanding advantages. Their high degree ofwater-solubility makes them particularly suitable for the preparation ofliquid dye concentrates which are preferred in the paper industry. Thesubject dyes are also less prone to "bleed" when paper impregnatedtherewith is wet and placed in contact with moist white paper. This is aparticularly desirable property for dyes designed for coloring paper tobe used in facial tissues, napkins and the like wherein it can beforeseen that the colored paper, wetted with common household liquidssuch as water, soap solutions, milk, carbonated beverages, and so forth,may come in contact with other surfaces, such as textiles, paper and thelike which should be protected from stain. Another advantageous propertyof these new water-soluble dyes for use in the paper trade is found intheir high degree of color discharge when bleached with hypochlorite or"chlorine" bleach. This property of dyes is particularly desired bypapermakers in order that dyed paper may be completely bleached prior toreprocessing. Still another advantageous property of the water-solubledyestuffs of this invention is found in their high resistance to achange of shade when used to color cellulosic materials, which haveeither previously been treated with or are treated subsequent todyeings, with wet-strength resin.

We have also found that the dyes of this invention have a high degree ofsubstantivity for bleached fiber such as is used in most coloreddisposable paper products. Moreover, they are absorbed by cellulosicfibers from aqueous solution at a very rapid rate. These properties areadvantageous to the paper industry, because it allows the dye to beadded to the pulp just prior to formation of the sheet.

The best mode contemplated by the inventor of carrying out thisinvention will now be described as to enable any person skilled in theart to which it pertains to make and use the same.

The novel dyestuffs of the invention are prepared by generally knownmethods, for example, by coupling the appropriate diazotized mono-,bis(aminomethyl)- or mono (2-aminoethyl)substituted aniline with theappropriate coupling component in an aqueous medium. In preparation ofthe compounds of Formula I, the ratio of the quantity of diazoniumcompound to coupling component is, of course, dependent on the number ofcoupling sites available in the coupling component. Thus when a singlecoupling site is present, for example, in a 2-hydroxy-3-naphthanilide,there is employed approximately one molecular proportion of thediazonium compound and when two coupling sites are available as, forexample, in 4,4'-bi-acetoacet-o-toluidide (Naphtol AS-G) there areemployed approximately two molecular proportions of the diazoniumcompound. Since the reaction temperature has some effect on the shade ofthe resulting water-insoluble azo dyestuffs, it is ordinarily desirableto maintain adequate control of the temperature of the reaction mixturein some predetermined manner. It is generally satisfactory to stir thereactants together at a temperature in the approximate range 0°-15° C.to effect only an incomplete coupling reaction, and then to warm themixture to a higher temperature, for instance in the approximate range25°-50° C., preferably at 30°-35° C., to complete the coupling reactionand develop the dyestuff. The reaction is begun in an alkaline aqueousmedium but the pH of the reaction mixture drops during the process to afinal value of about 5.0. After completion of the coupling reaction, thewater-insoluble basic azo dyestuffs can be isolated from the couplingmixture by filtration. The compounds thus obtained are readily convertedto water-soluble dyestuffs by treatment in an aqueous medium with atleast a stoichiometric quantity of an appropriate inorganic or organicacid as mentioned hereinbefore and the resultant dye can optionally beisolated or the aqueous solution in which it is formed can be adjustedto the desired concentration and used directly for dyeing operations.

The following compounds exemplify some of the azoic coupling componentsuseful for preparing the pigments of the invention.

3-Hydroxy-2-naphthanilide (Naphtol AS),

3-hydroxy-2',5'-dimethoxy-2-naphthanilide (Naphtol AS-BG),

3-hydroxy-3'-nitro-2-naphthanilide (Naphtol AS-BS),

3-hydroxy-2-naphtho-ortho-toluidide (Naphtol AS-D),

5'-chloro-3-hydroxy-2',4'-dimethoxy-2-naphthanilide (Naphtol AS-ITR),

4'-chloro-3-hydroxy-2',5'-dimethoxy-2-naphthanilide (Naphtol AS-LC),

3-hydroxy-2'-methyl-2-naphth-para-anisidide (Naphthol AS-LT),

3-hydroxy-2-naphtho-2,4-xylidide (Naphtol AS-MX),

3-hydroxy-2-naphth-ortho-anisidide (Naphtol AS-OL),

3-hydroxy-2-naphtho-ortho-phenetidide (Naphtol AS-PH),

3-hydroxy-2-naphth-para-anisidide (Naphtol AS-RL),

3-hydroxy-N-2-naphthyl-2-naphthamide (Naphtol AS-SW),

4'-chloro-3-hydroxy-2-naphtho-ortho-toluidide (Naphtol AS-TR),

3'-chloro-3-hydroxy-2-naphtho-ortho-toluidide (Naphthol AS-KB),

7-bromo-3-hydroxy-2-naphth-ortho-anisidide,

3'-Chloro-3-hydroxy-2-naphth-ortho-anisidide (Naphtol AS-NEL),

3-methyl-1-(p-tolyl)-5-hydroxypyrazole,

3-Methyl-1-(3-bromophenyl)-5-hydroxypyrazole,

3-Methyl-1-(4-iodophenyl)-5-hydroxypyrazole,

3-Methyl-1-(o-tolyl)-5-hydroxypyrazole,

3-Methyl-1-(4-chlorophenyl)-5-hydroxypyrazole,

3-Methyl-1-(2-ethoxy-5-nitrophenyl)-5-hydroxypyrazole,

3-Methyl-1-(2,4-dichlorophenyl)-5-hydroxypyrazole,

3-Methyl-1-(2,4-dinitrophenyl)-5-hydroxypyrazole,

3-Methyl-1-(2-methyl-4-iodophenyl)-5-hydroxypyrazole,

3-Methyl-1-(2,5-dimethylphenyl)-5-hydroxypyrazole,

3-Methyl-1-(2,4,6-trichlorophenyl)-5-hydroxypyrazole,

3-Methyl-1-phenyl-5-hydroxypyrazole,

3-Methyl-1-(4-methoxyphenyl)-5-hydroxypyrazole,

3-Methyl-1-(4-ethoxyphenyl)-5-hydroxypyrazole,

3-Methyl-1-(4-propoxyphenyl)-5-hydroxypyrazole,

3-Methyl-1-(3-nitrophenyl)-5-hydroxypyrazole,

3-Methyl-1-(4-nitrophenyl)-5-hydroxypyrazole,

3-Methyl-1-(2-chlorophenyl)-5-hydroxypyrazole,

4',4'''-Biacetoacetanilide,

4,4'-Bi-ortho-acetoacetotoluidide (Naphtol AS-G),

2',2'''-diiodo-4',4'''-biacetoacetanilide,

2',2'''-Dibromo-4',4'''-biacetoacetanilide,

2',2'''-Dichloro-4',4'''-biacetoacetanilide,

3',3'''-Diethoxy-4',4'''-biacetoacetanilide,

It will be obvious that those aryl moieties of the azoic couplingradicals represented by A in Formula I which are not shown bearingsubstituents represented by Q, Q¹ and Q² can also be substituted bygroups, represented by Q, Q¹ and Q², for example, lower-alkyl,lower-alkoxy and halogen.

The requisite diazotizable amines, which are anilines bearing one or twoaminomethyl groups or one 2-aminoethyl group on the ring are knownclasses of compounds which are either commercially available or can bereadily obtained by procedures well known in the prior art. For example,an appropriate aniline is interacted with approximately one molecularequivalent each of formaldehyde and phthalimide to obtain thecorresponding phthalimidomethyl aniline which is then subjected tohydrolysis to obtain the desired mono-aminomethyl-substitutedintermediate. The bis-aminomethylated intermediates are similarlyobtained by the interaction of an appropriate aniline with approximatelytwo molecular equivalents each of formaldehyde and phthalimide to obtainthe corresponding bis(phthalimidomethyl)aniline which is then hydrolyzedto obtain the desired bis(aminomethyl)aniline. The following compoundsare exemplary of ring aminomethylated anilines useful in the practice ofthis invention.

3-Aminomethylaniline,

4-Methyl-3-aminomethylaniline,

2-Methoxy-3-aminomethylaniline,

4-Methoxy-3-aminomethylaniline,

2-Methyl-5-aminomethylaniline,

2,3-Dimethyl-5-aminomethylaniline,

2-Isopropyl-5-methyl-3-aminomethylaniline,

3-Isopropyl-2-methoxy-5-aminomethylaniline,

4,5-Dimethoxy-2-propyl-3-aminomethylaniline,

3-Bromo-5-aminomethylaniline,

5-Isopropyl-2-methyl-3-aminomethylaniline,

5-Ethyl-2-methyl-3-aminomethylaniline,

3,4-Diethyl-5-aminomethylaniline,

3-Methoxy-4-methyl-5-aminomethylaniline,

3-Chloro-4-isopropyl-5-aminomethylaniline,

2,3,4-Trimethyl-5-aminomethylaniline,

2-Chloro-4,5-dimethoxy-3-aminomethylaniline,

5-Chloro-2,4-diethoxy-3-aminomethylaniline,

4,5-Dimethoxy-2-fluoro-3-aminomethylaniline,

2-Chloro-4-methoxy-5-methyl-3-aminomethylaniline,

2,5-Dichloro-4-methoxy-3-aminomethylaniline,

4-(2-Aminoethyl)aniline,

2-Methoxy-4-aminomethylaniline,

4-Aminomethylaniline,

2-Chloro-4-aminomethylaniline,

2-Ethoxy-4-aminomethylaniline,

5-Chloro-2-propyl-3-aminomethylaniline,

3,5-Bis(aminomethyl)aniline,

4-Methyl-3,5-bis(aminomethyl)aniline,

4-Methoxy-3,5-bis(aminomethyl)aniline,

2-Methoxy-3,5-bis(aminomethyl)aniline,

2,4-Diethyl-3,5-bis(aminomethyl)aniline,

2-Iodo-3,5-bis(aminomethyl)aniline,

4-Fluoro-3,5-bis(aminomethyl)aniline,

2-Methoxy-4-methyl-3,5-bis(aminomethyl)aniline,

2,4-Diisopropyl-3,5-bis(aminomethyl)aniline, and

4-Bromo-2-methoxy-3,5-bis(aminomethyl)aniline.

2-Bromo-4-aminomethylaniline.

The manner in which the new pigments and dyes of this invention areobtained and used is illustrated by the following examples without,however, being limited thereto. In the following examples, the term"parts" is in each instance used to indicate parts by weight and therelationship of parts by weight to parts by volume is the same as thatof the kilogram to the liter.

EXAMPLE 1

To a solution of 15.4 parts of 4-methoxy-3,5-bis(aminomethyl)anilinetrihydrochloride in 250 parts of water and 6 parts of concentratedhydrochloric acid were added 200 parts of crushed ice. The amine wasthen diazotized at a temperature between 0°-5° C. by adding a solutionof 4.2 parts of sodium nitrite in 30 parts of water. The reactionmixture was stirred at less than 5° C. for 30 minutes after which theexcess nitrate was removed by the gradual addition of sulfamic aciduntil nitrite ion could no longer be detected by testing withstarch-iodide paper. The cold solution was then made slightly alkalineto Congo Red paper by the addition of sodium acetate.

In a separate container, 14.7 parts of 3-hydroxy-2-naphth-o-anisidide(Naphtol AS-OL) were mixed with 46.5 parts of 2-ethoxyethanol, 94 partsof warm water, 8 parts of 50 percent aqueous solution of sodiumhydroxide and 0.033 parts of nonylphenoxypoly(ethyleneoxy)ethanol(Igepal® CO-630). The solution thus obtained was diluted with 310 partsof cold water and the cold diazonium solution obtained as describedabove was added in a thin stream to the diluted solution. The reactionmixture was stirred at 20°-25° C. until consumption of the diazoniumsalt was complete. Eleven parts of glacial acetic acid were added to theresulting red mixture, which was heated to 50° C. and filtered. Theclear red filtrate was made slightly alkaline to Brilliant Yellow paperby the addition of sodium carbonate whereupon a tacky red solidprecipitated. The solid was collected and washed with water and dried ina vacuum oven to obtain chiefly the red dyestuff having the formula##STR21##

The visible absorption spectrum of an aqueous acetic acid solution ofthis dyestuff, containing 0.02 g of dye per liter of solution showedmaxima at 503 millimicrons, A=0.848, and at 525 millimicrons, A=0.820.

A concentrated dye solution was prepared by adding 20 parts of thisdyestuff to a mixture of 11.4 parts of 70 percent glycolic acid, 8 partsof 2-(ethoxyethoxy)ethanol and 34 parts of water at a temperaturebetween 50° and 60° C. The mixture was stirred until solution wascomplete. Paper dyed with aqueous dilutions of this concentrate had ascarlet shade and was found to be highly bleachable, in the bleach testdescribed below. The dye was also found to bleed only slightly in thewater-bleed test and in the soap-bleed test when tested in accord withthe procedure described below.

Testing Procedures

The following test procedures were employed to determine the resistanceof the dyestuffs to bleed in moist paper, bleed from paper in thepresence of soap, and to bleaching with hypochlorite bleach.

Water "Bleed" Test

This procedure is a modification of the AATCC Standard Test Method15-1962, "Colorfastness to Perspiration".

Test pieces consisting of four plies, each one inch square, are cut fromthe dyed paper to be tested. One or more dyed papers of known dyemigration quality are included in the test series as standards.

The absorbent material consists of filter paper having a relativelysmooth finish (Whatman #1, 4.25 cm. dia. equivalent). In addition,smooth, flat, glass or clear plastic plates of adequate stiffness,measuring two inches wide and three inches long, are required asseparating plates. A 1,000 gram weight serves as a dead weight loading.

Four filter paper absorbent pieces are used for each dyed paper testsquare, two for each side.

The migration test "sandwich" is constructed as follows. A separatingplate is placed on a horizontal support and two pieces of the filterpaper placed centrally on this plate with the smoother side up. Thesquare dyed paper test pieces, held by tweezers, are immersed in tapwater at room temperature for five seconds, drained for five seconds,and immediately centered on the filter paper. Immediately, two pieces offilter paper are centered on the test square and followed at once byanother separating plate. This "sandwich" is pressed for a moment withthe fingers, after which, without delay, a piece of filter paper ispositioned on the top separating plate as before to receive a secondtest square of wetted dyed paper. The above procedure is then repeatedas rapidly as possible and without interruption, stacking one "sandwich"on the other, until all dyed paper test pieces have been put under test.

As soon as a stack is completed, a 1,000 gram weight is centered on thetop separating plate. The stack is allowed to stand at room temperature(75° F.) for fifteen minutes.

At the end of the migration period, the stack is disassembled, and eachdyed paper test square and its filter paper absorbents clipped to asupporting card. A separate card is used for each test square. The dyedpaper test squares and filter papers are air dried at room temperaturefor at least two hours (in the dark) before ranking. Relative degrees ofdye migration, as compared to that from standard samples, are determinedby visual ratings, in daylight, of the intensity of dye stain on thefilter paper surfaces which had been in contact with the test square.

Soap Bleed Test

This procedure utilizes the same method employed in the Water Bleed Testdescribed above, except that the dyed paper test squares are immersed ina 0.5 percent tap water solution of white soap flakes (a mixture of 80percent sodium soap and 20 percent potassium soap produced from 70percent tallow and 30 percent coconut oil glyceride blend; "Ivory"brand, Procter and Gamble Co.) at 120° F., instead of water alone.

Bleach Test

This procedure compares the degree to which the color of dyed paperswould be discharged in a waste paper recovery operation employinghypochlorite bleach.

A preliminary estimate of bleachability is obtained by placing a drop ofhypochlorite bleach, containing 2.5 percent available chlorine; on thedyed paper and allowing it to dry at room temperature. From this test,both rate and degree of bleaching are estimated.

A more accurate test, approximating paper mill procedure, is performedby defibering three grams of dyed paper in 150 ml of distilled waterusing a kitchen blender. The defibered pulp slurry is placed in a jarand hypochlorite is added to the extent desired, usually 2.5 percentavailable chlorine based on the weight of the dry fiber. The slurryconsisting of pulp and hypochlorite is adjusted to pH 9 with dilutesulfuric acid or dilute aqueous solution of sodium hydroxide and placedin a water bath to maintain the interval in the temperature range of115° F. to 125° F. After the test is started, the jar is loosely capped.At five minute intervals, the cap is tightened and the jar invertedtwice to circulate the liquor. The cap is loosened between inversions.After twenty minutes, the pH is checked and, if higher than 7.5, isadjusted thereto. The test is then continued for an additional twentyminutes (with five minutes between inversions). The terminal pH isgenerally found to be 6.0-6.5. An excess of sodium thiosulfate is addedas an antichlor, mixed for five minutes and the slurry is diluted to aconcentration of approximately 0.3 percent of fiber. Sheets are thenprepared at pH 7 without a washing step. Finally, this sheet is pressedand dried in a paper dryer. Control dyeings at specific levels can thenbe made to accurately determine the loss of strength of color onbleaching.

EXAMPLE 2

Following the procedure described in Example 1 above, 7.58 parts of2-methoxy-5-aminomethylaniline in a solution of 137 parts of water and12 parts of concentrated hydrochloric acid were diazotized with 3.5parts of sodium nitrite at 0° C. In a separate container 9.2 parts of4,4'-bi-acetoacet-o-toluidide (Naphtol AS-G) were mixed with 15.7 partsof isopropanol, 95 parts of water and 5.3 parts of 50 percent aqueoussolution of sodium hydroxide. A solution resulted which was then addedin a thin stream to the cold diazonium solution. The reaction mixturewas stirred at room temperature until there was no diazonium saltremaining. The solid product, which resulted, was collected byfiltration and dried in a vacuum oven. There was thus obtained a yellowdyestuff having the formula ##STR22##

The visible absorption spectrum of an aqueous acetic acid solution ofthis dyestuff, containing 0.02 g of the dye per liter of solution showeda maximum at 402 millimicrons, A=0.99.

A dye solution was prepared by thoroughly mixing one part of thisdyestuff with one part of acetic acid and diluting the resultant pasteof the acetic acid addition salt to a volume of one liter with water.Paper dyed with this solution had a yellow shade and was found to behighly bleachable and showed no bleed in the water-bleed test and in thesoap-bleed test.

EXAMPLE 3

Following the procedure described in Example 1 above, 15.4 parts of2-methoxy-3,5-bis(aminomethyl)aniline trihydrochloride in a solution of250 parts water and 6 parts of concentrated hydrochloric acid werediazotized with 3.5 parts of sodium nitrite at 0° C. In a separatecontainer, 5.8 parts of 6-amino-1-naphthol-3-sulfonic acid weredissolved in a solution of 100 parts of water and 7.9 parts of 50percent aqueous solution of sodium hydroxide. The solution was added ina thin stream to the cold diazonium solution. The reaction mixture wasallowed to warm to 30° C. and stirring was continued until there was nodiazonium salt remaining. The resulting dark solution was made slightlyalkaline to Brilliant Yellow paper and 100 parts of sodium chloride wereadded to precipitate the product. The separated solid was collected byfiltration and dried in a vacuum oven to obtain chiefly a brown dyestuffhaving the formula ##STR23##

The visible absorption spectrum of an aqueous acetic acid solution ofthis dyestuff, containing 0.02 g of the dye per liter of solution showeda maximum at 475 millimicrons, A=0.72.

A dye solution was prepared by thoroughly mixing one part of thisdyestuff with two parts of ten percent aqueous acetic acid and dilutingthe mixture to a volume of one liter with water. Paper dyed with thissolution had a brown shade and was found to be highly bleachable. Thedye was found to bleed only slightly in the water-bleed test and in thesoap-bleed test.

EXAMPLE 4

Following the procedure described in Example 1 above, 15.4 parts of2-methoxy-3,5-bis(aminomethyl)aniline trihydrochloride in a solution of250 parts of water and 6 parts of concentrated hydrochloric acid werediazotized with 3.5 parts of sodium nitrite at 0° C. In a separatecontainer, nine parts of 4,4'-bi-acetoacet-o-toluidide (Naphthol AS-G)were mixed with 15 parts of isopropanol, 90 parts of water and 5.3 partsof 50 percent aqueous solution of sodium hydroxide. A solution resultedwhich was then added in a thin stream to the cold diazonium solution.The reaction mixture was stirred at a temperature in the range of10°-15° C. for one hour and was then warmed to 30° C. Stirring at 30° C.was continued until the consumption of the diazonium salt was complete.The slurry was made slightly alkaline to Brilliant Yellow paper and theyellow product was collected by filtration, washed with water and driedin a vacuum oven to obtain chiefly a yellow dyestuff having the formula##STR24##

The visible absorption spectrum of an aqueous acetic acid solution ofthis dyestuff, containing 0.02 g of the dye per liter of solution showeda maximum at 387 millimicrons, A=1.324.

A concentrated dye dispersion was prepared by adding 18.5 parts of thisdyestuff to a mixture of 20 parts of acetic acid and 74 parts of waterat 60° C. The mixture was heated at 90° C. for one hour then cooled.Paper dyed with aqueous dilutions of this dye dispersion had a greenishyellow shade and was found to be highly bleachable. The dye was found tohave no bleed in the water-bleed test and in the soap-bleed test.

EXAMPLE 5

Following the procedure described in Example 1 above, 15.4 parts of4-methoxy-3,5-bis(aminomethyl)aniline trihydrochloride in a solution of250 parts water and 6 parts of concentrated hydrochloric acid werediazotized with 4.2 parts of sodium nitrite at 0° C. In a separatecontainer, nine parts of 4,4'-bi-acetoacet-o-toluidide (Naphtol AS-G)were mixed with 15 parts of methanol, 90 parts of water and 5.3 parts of50 percent aqueous solution of sodium hydroxide. A solution resultedwhich was then added in a thin stream to the cold diazonium solutionobtained as described above. The reaction mixture was stirred between10° and 15° C. for one hour and then was warmed to 30° C. Stirring at30° C. was continued until consumption of the diazonium salt wascomplete. The slurry which resulted was made slightly alkaline toBrilliant Yellow paper by the addition of sodium carbonate and theproduct was collected by filtration and washed with water. The productwas dried in a vacuum oven to obtain chiefly a yellow dyestuff havingthe formula ##STR25##

The visible absorption spectrum of an aqueous acetic acid solution ofthis dyestuff containing 0.02 g of the dye per liter of solution showeda maximum at 384 millimicrons, A=1.394.

A concentrated dye solution was prepared by adding seven parts of thisdyestuff to a mixture of 3.5 parts of acetic acid and 24 parts of waterat a temperature between 70° and 80° C. The mixture was stirred untilthe solution was complete. Paper dyed with aqueous dilutions of this dyeconcentrate had a greenish yellow shade and was found to be highlybleachable. The dye was found to bleed only slightly in the water-bleedand in the soap-bleed test.

A concentrated dye solution was also prepared by mixing 115 parts of adyestuff paste containing approximately 7 parts of this dyestuff and 108parts of water with 10.2 parts of a 70 percent aqueous methanesulfonicacid solution and 60 parts of water. The resulting mixture was heated toapproximately 60° C., cooled to ambient temperature and the insolublesremoved by filtration. The filtrate showed a maximum in the visibleabsorption spectrum at 385 millimicrons.

The following table lists further Examples of additional azo dyestuffsof this invention prepared by diazotizing the amines shown in the secondcolumn of the table and coupling the resulting diazo compounds with thecoupling components shown in the third column of the table followingprocedures similar to those described in Examples 1-5 above. Theindicated shades are obtained when aqueous solutions of theacid-addition salt forms of the dyestuffs are used for dyeing cellulose.

    __________________________________________________________________________    Example                                                                            Diazotized Coupling                                                      No.  Amine      Component    Shade                                            __________________________________________________________________________    6    4-methyl-3-amino-                                                                        4,4'-bi-ortho-aceto-                                                                       Greenish-                                             Methylaniline                                                                            acetotoluidide (Naph-                                                                      Yellow                                                           tol AS-G)                                                     7    "          5'-chloro-3-hydroxy-                                                                       Red                                                              2',4'-dimethoxy-2-                                                            naphthanilide (Naph-                                                          tol AS-ITR)                                                   8    "          3-methyl-1-(p-tolyl)-                                                                      Reddish-                                                         5-hydroxypyrozole                                                                          Yellow                                           9    "          3'-chloro-3-hydroxy-                                                                       red                                                              2-naphth-ortho-anis-                                                          idide (Naphtol AS-NEL)                                        10   "          4',4'"-biacetoacet-                                                                        Yellow                                                           anilide                                                       11   4-methoxy-3-amino-                                                                       3-hydroxy-2-naphtho-                                                                       Red                                                   methlyaniline                                                                            ortho-anisidide (Naph-                                                        tol AS-OL)                                                    12   "          2',2'"-dichloro-4',                                                                        Greenish-                                                        4'"-biacetoacet-                                                                           Yellow                                                           anilide                                                       13   "          3-methyl-1-(p-tolyl)-                                                                      Reddish-                                                         5-hydroxypyrazole                                                                          Yellow                                           14   "          4'-chloro-3-hydroxy-                                                                       Red                                                              2',5'-dimethoxy-2-                                                            naphthanilide (Naph-                                                          tol AS-LC)                                                    15   4-methyl-3,5-bis-                                                                        3-hydroxy-2-naphth-                                                                        Red                                                   (aminomethyl)-                                                                           ortho-anisidide                                                    aniline    (Naphtol AS-OL)                                               16   "          2',2'"-dichloro-4',                                                                        Greenish-                                                        4'"-biacetacet-                                                                            Yellow                                                           anilide                                                       17   "          3-methyl-1-(p-tolyl)-                                                                      Reddish-                                                         5-hydroxypyrazole                                                                          Yellow                                           18   "          4'-chloro-3-hydroxy-                                                                       Scarlet                                                          2',5'-dimethoxy-2-                                                            naphthanilide (Naph-                                                          tol AS-LC)                                                    19   "          4',4'"-biacetoacet-                                                                        Greenish-                                                        anilide      Yellow                                           20   4-methoxy-3,5-bis-                                                                       3-hydroxy-3'-nitro-                                                                        Red                                                   (aminomethyl)aniline                                                                     2-naphthanilide                                                               (Naphtol AS-BS)                                               21   "          3-hydroxy-2-naphth-                                                                        Scarlet                                                          anilide (Naphtol AS)                                          22   "          3-hydroxy-N-2-naph-                                                                        Scarlet                                                          thyl-2-naphthamide                                                            (Naphtol AS-SW)                                               23   "          3'-chloro-3-hydroxy-                                                                       Scarlet                                                          2-naphth-ortho-anis-                                                          idide (Naphtol AS-NEL)                                        24   "          5'-chloro-3-hydroxy-                                                                       Bluish-                                                          2',4'-dimethoxy-2-                                                                         Red                                                              naphthanilide (Naph-                                                          tol AS-ITR)                                                   25   "          3-methyl-1-phenyl-5-                                                                       Reddish-                                                         hydroxypyrozole                                                                            Yellow                                           26   2-methoxy-3,5-bis                                                                        3-hydroxy-2-naphth-                                                                        Scarlet                                               (aminomethyl)ani-                                                                        anilide (Naphtol AS)                                               line                                                                     27   "          3-hydroxy-2-naphth-                                                                        Scarlet                                                          ortho-anisidide                                                               (Naphtol AS-OL)                                               28   "          3-hydroxy-2-naphth-                                                                        Scarlet                                                          para-anisidide                                                                (Naphtol AS-RL)                                               29   "          3'-chloro-3-hydroxy-                                                                       Scarlet                                                          2-naphth-ortho-anis-                                                          idide (Naphtol AS-NEL)                                        30   "          3-hydroxy-3'-nitro-                                                                        Red                                                              2-naphthanilide (Naph-                                                        tol AS-BS)                                                    31   "          2-naphtol    Orange                                           32   "          3-methyl-1-(p-tolyl)-                                                                      Yellow                                                           5-hydroxypyrazole                                             33   3-aminomethylani-                                                                        3-hydroxy-2-naphth-                                                                        Scarlet                                               line       anilide (Naphtol AS)                                          34   "          3'-chloro-3-hydroxy-                                                                       Scarlet                                                          2-naphth-ortho-anis-                                                          idide (Naphtol AS-NEL)                                        35   "          2',2'"-dibromo-4',                                                                         Yellow                                                           4'"-biacetoacetani-                                                           lide                                                          36   "          4'-chloro-3-hydroxy-                                                                       Red                                                              2-naphtho-ortho-tolu-                                                         idide (Naphtol AS-TR)                                         37   "          4',4'"-biacetoacet-                                                                        Yellow                                                           anilide                                                       38   "          3-methyl-1-(4-meth-                                                                        Reddish-                                                         oxyphenyl)-5-hy-                                                                           Yellow                                                           droxypyrazole                                                 39   2-methoxy-3-amino-                                                                       3'-chloro-3-hydroxy-                                                                       Red                                                   methylaniline                                                                            2-naphth-ortho-anis-                                                          idide (Naphtol AS-NEL)                                        40   "          3-hydroxy-2'-methyl-                                                                       Red                                                              2-naphth-para-anisi-                                                          dide (Naphtol AS-LT)                                          41   "          3',3'"-diethoxy-4',                                                                        Yellow                                                           4'"-biacetoacetani-                                                           lide                                                          42   "          7-bromo-3-hydroxy-2-                                                                       Red                                                              naphth-ortho-anisi-                                                           dide                                                          43   "          4',4'"-biacetoacet-                                                                        Yellow                                                           anilide                                                       44   "          3-methyl-1-(4-ethoxy-                                                                      Reddish-                                                         phenyl)-5-hydroxy-                                                                         Yellow                                                           pyrazole                                                      45   2-methyl-5-amino-                                                                        2',2'"-diiodo-4',                                                                          Yellow                                                methylaniline                                                                            4'"-biacetoacet-                                                              anilide                                                       46   "          3'-chloro-3-hydroxy-                                                                       Red                                                              2-naphth-ortho-anis-                                                          idide (Naphtol AS-NEL)                                        47   "          3-hydroxy-2',5'-di-                                                                        Bluish-                                                          methoxy-2-naphth-                                                             anilide (Naphtol AS-                                                          BG)                                                           48   "          2',2'"-dichloro-4',                                                                        Greenish-                                                        4'"-biacetoacetani-                                                                        Yellow                                                           lide                                                          49   "          3-methyl-1-(4-pro-                                                                         Reddish-                                                         poxyphenyl)-5-hydroxy-                                                                     Yellow                                                           pyrazole                                                      50   2,3-dimethyl-5-                                                                          3'-chloro-3-hydroxy-                                                                       Red                                                   aminomethylani-                                                                          2-naphtho-ortho-tolui-                                             line       dide (Naphtol AS-KB)                                          51   "          3-hydroxy-3'-nitro-                                                                        Bluish-                                                          2-naphthanilide                                                                            Red                                                              (Naphtol AS-BS)                                               52   "          5'-chloro-3-hydroxy-                                                                       Bluish-                                                          2',4'-dimethoxy-2-                                                                         Red                                                              naphthanilide (Naph-                                                          tol AS-ITR)                                                   53   "          3'-chloro-3-hydroxy-                                                                       Red                                                              2-naphth-ortho-anis-                                                          idide (Naphtol AS-NEL)                                        54   "          4',4'"-biacetoacet-                                                                        Yellow                                                           anilide                                                       55   "          3-methyl-1-(3-nitro-                                                                       Reddish-                                                         phenyl)-5-hydroxy-                                                                         Yellow                                                           pyrazole                                                      56   2-isopropyl-5-                                                                           3-hydroxy-2-naphtho-                                                                       Red                                                   methyl-3-amino-                                                                          ortho-toluidide (Naph-                                             methylaniline                                                                            tol AS-D)                                                     57   "          4,4'-bi-ortho-aceto-                                                                       Yellow                                                           acetotoluidide (Naph-                                                         tol AS-G)                                                     58   "          3',3'"-diethoxy-4',                                                                        Reddish-                                                         4'"-biacetoacet-                                                                           Yellow                                                           anilide                                                       59   "          3-methyl-1-(p-tolyl)-                                                                      Reddish-                                                         5-hydroxypyrazole                                                                          Yellow                                           60   3-isopropyl-2-meth-                                                                      3-hydroxy-2-naphtho-                                                                       Red                                                   oxy-5-aminomethyl-                                                                       2,4-xylidide (Naph-                                                aniline    tol AS-MX)                                                    61   "          2',2'"-dichloro-4',                                                                        Yellow                                                           4'"-biacetoacet-                                                              anilide                                                       62   "          5'-chloro-3-hydroxy-                                                                       Bluish-                                                          2',4'-dimethoxy-2-                                                                         Red                                                              naphthanilide (Naph-                                                          tol AS-ITR)                                                   63   "          7-bromo-3-hydroxy-                                                                         Red                                                              2-naphth-ortho-                                                               anisidide                                                     64   "          3-methyl-1-(4-nitro-                                                                       Reddish-                                                         phenyl)-5-hydroxy-                                                                         Yellow                                                           pyrazole                                                      65   4,5-dimethoxy-2-                                                                         3-hydroxy-2-naphtho-                                                                       Red                                                   propyl-3-amino-                                                                          ortho-phenetidide                                                  methylaniline                                                                            (Naphtol AS-PH)                                               66   "          2',2'"-dibromo-4',                                                                         Yellow                                                           4'"-biacetoacet-                                                              anilide                                                       67   "          3-hydroxy-N-2-naph-                                                                        Bluish-                                                          thyl-2-naphthamide                                                                         Red                                                              (Naphtol AS-SW)                                               68   "          4'-chloro-3-hydroxy-                                                                       Red                                                              2-naphtho-ortho-tolu-                                                         idide (Naphtol AS-TR)                                         69   "          4',4'"-biacetoacet-                                                                        Yellow                                                           anilide                                                       70   "          3-methyl-1-(2-chloro-                                                                      Reddish-                                                         phenyl)-5-hydroxy-                                                                         Yellow                                                           pyrazole                                                      71   3-bromo-5-amino-                                                                         3-hydroxy-2-naphth-                                                                        Red                                                   methylaniline                                                                            para-anisidide                                                                (Naphtol AS-RL)                                               72   "          4'-chloro-3-hydroxy-                                                                       Bluish-                                                          2',5'-dimethoxy-2-                                                                         Red                                                              naphthanilide (Naph-                                                          tol AS-LC)                                                    73   "          3-hydroxy-N-2-naph-                                                                        Bluish-                                                          thyl-2-naphthamide                                                                         Red                                                              (Naphtol AS-SW)                                               74   "          3'-chloro-3-hydroxy-                                                                       Red                                                              2-naphth-ortho-anis-                                                          idide (Naphtol AS-NEL)                                        75   "          3-methyl-1-(3-bromo-                                                                       Reddish-                                                         phenyl)-5-hydroxy-                                                                         Yellow                                                           pyrazole                                                      76   5-isopropyl-2-                                                                           4'-chloro-3-hydroxy-                                                                       Red                                                   methyl-3-amino-                                                                          2-naphtho-ortho-tolu-                                              methylaniline                                                                            idide (Naphtol AS-TR)                                         77   "          2',2'"-diiodo-4',                                                                          Reddish-                                                         4'"-biacetoacet-                                                                           Yellow                                                           anilide                                                       78   "          3-methyl-1-(p-tolyl)-                                                                      Reddish-                                                         5-hydroxypyrazole                                                                          Yellow                                           79   "          4,4'-bi-ortho-aceto-                                                                       Yellow                                                           acetotoluidide (Naph-                                                         tol AS-G)                                                     80   5-ethyl-2-methyl-                                                                        3-hydroxy-2-naphtho-                                                                       Red                                                   3-aminomethylani-                                                                        2,4-xylidide (Naph-                                                line       tol AS-MX)                                                    81   "          3'-chloro-3-hydroxy-                                                                       Red                                                              2-naphth-ortho-anis-                                                          idide                                                         82   "          2',2'"-dibromo-4',                                                                         Yellow                                                           4'"-biacetoacetanilide                                        83   "          3',3'"-diethoxy-4',                                                                        Yellow                                                           4'"-biacetoacet-                                                              anilide                                                       84   "          3-methyl-1-(4-iodo-                                                                        Orange                                                           phenyl)-5-hydroxy-                                                            pyrazole                                                      85   3,4-diethyl-5-amino-                                                                     3-methyl-1-(p-tolyl)-                                                                      Reddish-                                              methylaniline                                                                            5-hydroxypyrazole                                                                          Yellow                                           86   "          3'-chloro-3-hydroxy-                                                                       Red                                                              2-naphth-ortho-anis-                                                          idide (Naphtol AS-NEL)                                        87   "          2',2'"-dichloro-4',                                                                        Greenish-                                                        4'"-biacetoacet-                                                                           Yellow                                                           anilide                                                       88   "          3-hydroxy-2',5'-di-                                                                        Bluish-                                                          methoxy-2-naphth-                                                                          Red                                                              anilide (Naphtol AS-                                                          BG)                                                           89   3-methoxy-4-methyl-                                                                      3-hydroxy-2-naphth-                                                                        Red                                                   5-aminomethylaniline                                                                     anilide (Naphtol AS)                                          90   "          7-bromo-3-hydroxy-2-                                                                       Red                                                              naphth-ortho-anisi-                                                           dide                                                          91   "          2',2'"-diiodo-4',                                                                          Reddish-                                                         4'"-biacetoacet-                                                                           Yellow                                                           anilide                                                       92   "          3-methyl-1-(p-tolyl)-                                                                      Reddish-                                                         5-hydroxypyrazole                                                                          Yellow                                           93   3-chloro-4-iso-                                                                          3-hydroxy-3'-nitro-                                                                        Bluish-                                               propyl-5-amino-                                                                          2-naphthanilide                                                                            Red                                                   methylaniline                                                                            (Naphtol AS-BS)                                               94   "          5'-chloro-3-hydroxy-                                                                       Bluish-                                                          2',4'-dimethoxy-2-                                                                         Red                                                              naphthanilide (Naph-                                                          tol AS-ITR)                                                   95   "          7-bromo-3-hydroxy-2-                                                                       Red                                                              naphth-ortho-anisi-                                                           dide                                                          96   "          2',2'"-dibromo-4',                                                                         Yellow                                                           4'"-biacetoacet-                                                              anilide                                                       97   "          3-methyl-1-(o-tolyl)-                                                                      Reddish-                                                         5-hydroxypyrazole                                                                          Yellow                                           98   2,3,4-trimethyl-5-                                                                       3-hydroxy-2-naphtho-                                                                       Red                                                   aminomethylaniline                                                                       ortho-toluidide (Naph-                                                        tol AS-D)                                                     99   "          3'-chloro-3-hydroxy-                                                                       Red                                                              2-naphth-ortho-anis-                                                          idide (Naphtol AS-NEL)                                        100  "          4,4'-di-ortho-aceto-                                                                       Yellow                                                           acetotoluidide (Naph-                                                         tol AS-G)                                                     101  "          3-methyl-1-(p-tolyl)-                                                                      Reddish-                                                         5-hydroxypyrazole                                                                          Yellow                                           102  "          4',4'"-biacetoacet-                                                                        Yellow                                                           anilide                                                       103  2-chloro-4,5-di-                                                                         3-hydroxy-2-naphth-                                                                        Red                                                   methoxy-3-amino-                                                                         para-anisidide                                                     methylaniline                                                                            (Naphtol AS-RL)                                               104  "          7-bromo-3-hydroxy-2-                                                                       Bluish-                                                          naphth-ortho-anisi-                                                                        Red                                                              dide                                                          105  "          3'-chloro-3-hydroxy-                                                                       Red                                                              2-naphth-ortho-anis-                                                          idide (Naphtol AS-NEL)                                        106  "          3-methyl-1-(4-chloro-                                                                      Reddish-                                                         phenyl)-5-hydroxy-                                                                         Yellow                                                           pyrazole                                                      107  5-chloro-2,4-di-                                                                         3-hydroxy-2'-methyl-                                                                       Red                                                   ethoxy-3-amino-                                                                          2-naphth-para-anisi-                                               methylaniline                                                                            dide (Naphtol AS-LT)                                          108  "          2',2'"-dichloro-4',                                                                        Yellow                                                           4'"-biacetoacet-                                                              anilide                                                       109  "          3',3'"-diethoxy-4',                                                                        Yellow                                                           4'"-biacetoacet-                                                              anilide                                                       110  "          3-methyl-1-(p-tolyl)-                                                                      Reddish-                                                         5-hydroxypyrazole                                                                          Yellow                                           111  4,5-dimethoxy-2-                                                                         3-hydroxy-2-naphtho-                                                                       Red                                                   fluoro-3-amino-                                                                          ortho-phenetidide                                                  methylaniline                                                                            (Naphtol AS-PH)                                               112  "          3-hydroxy-2-naphth-                                                                        Red                                                              anilide (Naphtol AS)                                          113  "          2',2'"-dibromo-4',                                                                         Reddish-                                                         4'"-biacetoacet-                                                                           Yellow                                                           anilide                                                       114  "          3'-chloro-3-hydroxy-                                                                       Red                                                              2-naphth-ortho-anis-                                                          idide (Naphtol AS-NEL)                                        115  "          3-methyl-1-(2-eth-                                                                         Reddish-                                                         oxy-5-nitrophenyl)-                                                                        Yellow                                                           5-hydroxypyrazole                                             116  2-chloro-4-methoxy-                                                                      3-hydroxy-2-naphth-                                                                        Red                                                   5-methyl-3-amino-                                                                        anilide (Naphtol AS)                                               methylaniline                                                            117  "          3-hydroxy-2-naphtho-                                                                       Red                                                              ortho-phenetidide                                                             (Naphtol AS-PH)                                               118  "          3-methyl-1-(p-tolyl)-                                                                      Reddish-                                                         5-hydroxypyrazole                                                                          Yellow                                           119  "          5'-chloro-3-hydroxy-                                                                       Red                                                              2',4'-dimethoxy-2-                                                            naphthanilide (Naph-                                                          tol AS-ITR)                                                   120  "          4',4'"-biacetoacet-                                                                        Yellow                                                           anilide                                                       121  2,5-dichloro-4-                                                                          7-bromo-3-hydroxy-2-                                                                       Red                                                   methoxy-3-amino-                                                                         naphth-ortho-anisi-                                                methylaniline                                                                            dide                                                          122  "          3',3'"-diethoxy-4',                                                                        Yellow                                                           4'"-biacetoacet-                                                              anilide                                                       123  "          4,4'-bi-ortho-aceto-                                                                       Reddish-                                                         acetotoluidide (Naph-                                                                      Yellow                                                           tol AS-G)                                                     124  "          3'-chloro-3-hydroxy-                                                                       Red                                                              2-naphth-ortho-anis-                                                          idide (Naphtol AS-NEL)                                        125  "          3-methyl-1-(2,4-di-                                                                        Yellow                                                           chlorophenyl)-5-                                                              hydroxypyrazole                                               126  5-chloro-2-propyl-                                                                       4'-chloro-3-hydroxy-                                                                       Bluish-                                               3-aminomethylani-                                                                        2',5'-dimethoxy-2-                                                                         Red                                                   line       naphthanilide (Naph-                                                          tol AS-LC)                                                    127  "          3-methyl-1-(p-tolyl)-                                                                      Reddish-                                                         5-hydroxypyrazole                                                                          Yellow                                           128  "          2',2'"-dichloro-4',                                                                        Yellow                                                           4'"-biacetoacet-                                                              anilide                                                       129  "          3-hydroxy-2-naphth-                                                                        Red                                                              ortho-anisidide                                                               (Naphtol AS-OL)                                               130  3,5-bis(aminomethyl)-                                                                    3-methyl-1-(p-tolyl)-                                                                      Reddish-                                              aniline    5-hydroxypyrazole                                                                          Yellow                                           131  "          3-hydroxy-2',5'-di-                                                                        Red                                                              methoxy-2-naphth-                                                             anilide (Naphtol                                                              AS-BG)                                                        132  "          3'-chloro-3-hydroxy-                                                                       Scarlet                                                          2-naphth-ortho-anis-                                                          idide (Naphtol AS-NEL)                                        133  "          2',2'"-diiodo-4',                                                                          Yellow                                                           4'"-biacetoacet-                                                              anilide                                                       134  2,4-diethyl-3,5-bis-                                                                     3'-chloro-3-hydroxy-                                                                       Scarlet                                               (aminoethyl)aniline                                                                      2-naphth-ortho-anisi-                                                         dide (Naphtol AS-NEL)                                         135  "          5'-chloro-3-hydroxy-                                                                       Red                                                              2',4'-dimethoxy-2-                                                            naphthanilide (Naph-                                                          tol AS-ITR)                                                   136  "          3-hydroxy-3'-nitro-2-                                                                      Red                                                              naphthanilide (Naph-                                                          tol AS-BS)                                                    137  "          3'-chloro-3-hydroxy-                                                                       Scarlet                                                          2-naphtho-ortho-tolu-                                                         idide (Naphtol AS-KB)                                         138  "          4',4'"-biacetoacet-                                                                        Greenish-                                                        anilide      Yellow                                           139  "          3-methyl-1-(2,4-di-                                                                        Orange                                                           nitrophenyl)-5-                                                               hydroxypyrazole                                               140  2-iodo-3,5-bis-                                                                          3-methyl-1-(p-tolyl)-                                                                      Reddish-                                              (aminomethyl)-                                                                           5-hydroxypyrazole                                                                          Yellow                                                aniline                                                                  141  "          3',3'"-diethoxy-4',                                                                        Yellow                                                           4'"-biacetoacet-                                                              anilide                                                       142  "          4,4'-bi-ortho-aceto-                                                                       Greenish-                                                        acetotoluidide (Naph-                                                                      Yellow                                                           tol AS-G)                                                     143  "          4'-chloro-3-hydroxy-                                                                       Bluish-                                                          2',5'-dimethoxy-2-                                                                         Red                                                              naphthanilide (Naph-                                                          tol AS-LC)                                                    144  4-fluoro-3,5-bis-                                                                        2',2'"-dichloro-4',                                                                        Greenish-                                             (aminomethyl)ani-                                                                        4'"-biacetoacet-                                                                           Yellow                                                line       anilide                                                       145  "          3-hydroxy-2-naph-                                                                          Scarlet                                                          tho-2,4-xylidide                                                              (Naphtol AS-MX)                                               146  "          3-hydroxy-2-naphth-                                                                        Red                                                              ortho-anisidide                                                               (Naphtol AS-OL)                                               147  "          5'-chloro-3-hydroxy-                                                                       Red                                                              2',4'-dimethoxy-2-                                                            naphthanilide (Naph-                                                          tol AS-ITR)                                                   148  "          3-methyl-1-(2-methyl-                                                                      Reddish-                                                         4-iodophenyl)-5-                                                                           Yellow                                                           hydroxypyrazole                                               149  2-methoxy-4-methyl-                                                                      4'-chloro-3-hydroxy-                                                                       Scarlet                                               3,5-bis(aminometh-                                                                       2-naphtho-ortho-tolu-                                              yl)aniline idide (Naphtol AS-TR)                                         150  "          3-hydroxy-N-2-naph-                                                                        Red                                                              thyl-2-naphthamide                                                            (Naphtol AS-SW)                                               151  "          2',2'"-dibromo-4',                                                                         Yellow                                                           4'"-biacetoacet-                                                              anilide                                                       152  "          3-hydroxy-2-naphtho-                                                                       Scarlet                                                          ortho-phenetidide                                                             (Naphtol AS-PH)                                               153  "          3-methyl-1-(2,5-di-                                                                        Reddish-                                                         methylphenyl)-5-                                                                           Yellow                                                           hydroxypyrazole                                               154  2,4-diisopropyl-                                                                         3'-chloro-3-hydroxy-                                                                       Scarlet                                               3,5-bis(amino-                                                                           2-naphth-ortho-anis-                                               methyl)aniline                                                                           idide (Naphtol AS-NEL)                                        155  "          4'-chloro-3-hydroxy-                                                                       Red                                                              2',5'-dimethoxy-2-                                                            naphthanilide (Naph-                                                          tol AS-LC)                                                    156  "          3-hydroxy-2-naphth-                                                                        Scarlet                                                          para-anisidide (Naph-                                                         tol AS-RL)                                                    157  "          3-methyl-1-(p-tolyl)-                                                                      Reddish-                                                         5-hydroxypyrazole                                                                          Yellow                                           158  "          4',4'"-biacetoacet-                                                                        Greenish-                                                        anilide      Yellow                                           159  4-bromo-2-methoxy-                                                                       7-bromo-3-hydroxy-                                                                         Red                                                   3,5-bis(aminometh-                                                                       2-naphth-ortho-                                                    yl)aniline anisidide                                                     160  "          3-hydroxy-2-naphth-                                                                        Scarlet                                                          anilide (Naphtol AS)                                          161  "          2',2'"-diiodo-4',                                                                          Yellow                                                           4'"-biacetoacet-                                                              anilide                                                       162  "          3'-chloro-3-hydroxy-                                                                       Red                                                              2-naphth-ortho-anis-                                                          idide (Naphtol AS-NEL)                                        163  "          3-methyl-1-(2,4,6-tri-                                                                     Yellow                                                           chlorophenyl)-5-                                                              hydroxypyrazole                                               __________________________________________________________________________

EXAMPLE 164

Following the procedure described in Example 1 above, 4.3 parts of4-aminomethylaniline dihydrochloride in a solution of 100 parts of waterand 2.4 parts of concentrated hydrochloric acid were diazotized with 1.5parts of sodium nitrite dissolved in 12 parts of water at 0°-5° C. In aseparate container, 5.9 parts of 3-hydroxy-2-naphth-o-anisidide (NaphtolAS-OL) was mixed with 38 parts of hot water, 18.6 parts ofethoxyethanol, 2 drops of nonylphenoxypoly(ethyleneoxy)ethanol (Igepal®CO-630) and 3.1 parts of 50 percent aqueous sodium hydroxide. To thesolution thus obtained, there was added in a thin stream the colddiazonium solution prepared as described above. The reaction mixture wasstirred at ambient temperature until the consumption of the diazoniumsalt was complete. The slurry was made slightly alkaline to BrilliantYellow test paper and the red product which separated was collected byfiltration, washed with 200 parts of a one percent aqueous sodiumchloride solution and dried in a vacuum oven to obtain a red dyestuffhaving the formula ##STR26##

The visible absorption spectrum of a solution consisting of 0.02 g ofthe dyestuff dissolved in 200 ml of dimethylformamide diluted to oneliter with an aqueous solution of one percent Igepal® CO-630 andcontaining 3 drops of glacial acetic acid showed a maximum at 500millimicrons, A=0.8656.

A concentrated dye solution was prepared by dissolving one part of thedyestuff in 200 ml of dimethylformamide and 3 drops of glacial aceticacid and then diluting this solution to a total volume of one liter withwater. Paper dyed with this solution had a yellow-scarlet shade and wasfound to be highly bleachable. The dye was found to bleed only slightlyin the water-bleed test.

EXAMPLE 165

Following the procedure described in Example 1 above, 4.3 parts of3-aminomethylaniline dihydrochloride in a solution of 100 parts of waterand 2.4 parts of concentrated hydrochloric acid were diazotized with 1.5parts of sodium nitrite at 0° to 5° C. In a separate container 5.9 partsof 3-hydroxy-2-naphth-o-anisidide (Naphtol AS-OL) were dissolved in asolution of 38 parts hot water, 18.6 parts of ethoxyethanol, 2 drops ofnonylphenoxypoly(ethyleneoxy)ethanal (Igepal® CO-630) and 3.1 parts of50 percent aqueous sodium hydroxide. To the resulting solution there wasthen added in a thin stream the cold diazonium solution prepared asdescribed above. The reaction mixture was stirred at room temperatureuntil the consumption of the diazonium salt was complete. The resultingsolution was made slightly alkaline to Brilliant Yellow test paper bythe addition of approximately 2.3 parts of concentrated aqueous ammoniaand the solid which separated was collected by filtration, washed with200 parts of one percent aqueous sodium chloride solution and dried in avacuum oven to obtain a red dyestuff having the formula ##STR27##

The visible absorption spectrum of an aqueous acetic acid solution ofthis dyestuff, containing 0.02 g of the dye per liter of solution showeda maximum at 498 millimicrons, A=0.756.

A dye solution was prepared by dissolving 1.0 g of this dyestuff in 200ml of dimethylformamide and 3 drops of glacial acetic acid and thendiluting the solution to a volume of one liter with water. Paper dyedwith this solution had a yellow-scarlet shade and was found to be highlybleachable. The dye was found to bleed only slightly in the water-bleedtest.

EXAMPLE 166

Following the procedure described in Example 1 above, 2.72 parts of4-(2-aminoethyl)aniline in a mixture of 100 parts of water, 7.14 partsof concentrated hydrochloric acid and 80 parts of crushed ice werediazotized at 0°-5° C. with 1.5 parts of sodium nitrite dissolved in 12parts of water. In a separate container 5.9 parts of3-hydroxy-2-naphth-o-anisidide (Naphtol AS-OL) were mixed with 18.6parts of 2-ethoxyethanol, 38 parts of hot water and 3.1 parts of 50percent aqueous sodium hydroxide. To the resulting solution was thenadded in a thin stream the cold diazonium solution prepared as describedabove. The reaction mixture was stirred at ambient temperature until nodiazonium salt remained. The resulting solution was made slightlyalkaline to Brilliant Yellow paper by the addition of aqueous ammoniaand the solid product which resulted was collected by filtration anddried in a vacuum oven. There was thus obtained a red dyestuff havingthe formula ##STR28##

The visible absorption spectrum of an aqueous acetic acid solution ofthis dyestuff, containing 0.02 g of the dye per liter of solution showeda maximum at 504 millimicrons, A=0.8176.

A dye solution was prepared by thoroughly mixing one part of thisdyestuff with five parts of 10 percent acetic acid and diluting theresultant paste of the acetic acid addition salt to a volume of oneliter with water. Paper dyed with this solution had a yellow-scarletshade and was found to be highly bleachable. The dye was found to bleedonly slightly in the water-bleed and in the soap-bleed test.

The following table lists further Examples of additional azo dyestuffsof this invention prepared by diazotizing the amines shown in the secondcolumn of the table and coupling the resulting diazo compounds with thecoupling components shown in the third column of the table followingprocedures similar to those described in Examples 1-5 above. Theindicated shades are obtained when aqueous solutions of theacid-addition salt forms of the dyestuffs are used for dyeing cellulose.

    ______________________________________                                        Ex.  Diazotized    Coupling                                                   No.  Amine         Component      Shade                                       ______________________________________                                        167  3-methoxy-4-amino-                                                                          3-hydroxy-2-naphth-                                                                          Red                                              methylaniline ortho-anisidide                                                               (Naphtol AS-OL)                                            168  "             2',2'"-dichloro-'4-                                                                          Yellow                                                         4'"-biacetoacet-                                                              anilide                                                    169  "             3-methyl-1-(p-tolyl)-                                                                        Reddish-                                                       5-hydroxypyrazole                                                                            Yellow                                      170  "             4'-chloro-3-hydroxy-                                                                         Red                                                            2',5'-dimethoxy-2-                                                            naphthanilide (Naph-                                                          tol AS-LC)                                                 171  4-(2-aminoethyl)-                                                                           2',2'"-dichloro-4',                                                                          Greenish-                                        aniline       4'"-biacetoacet-                                                                             Yellow                                                         anilide                                                    172  "             3-methyl-1-(p-tolyl)-                                                                        Yellow                                                         5-hydroxypyrazole                                          173  "             4'-chloro-3-hydroxy-                                                                         Scarlet                                                        2',5'-dimethoxy-2-                                                            naphthanilide (Naph-                                                          tol AS-LC)                                                 174  "             4',4'"-biacetoacet-                                                                          Greenish-                                                      anilide        Yellow                                      175  3-bromo-4-amino-                                                                            4,4'-bi-ortho-aceto-                                                                         Greenish-                                        methylaniline acetotoluidide (Naph-                                                                        Yellow                                                         tol AS-G)                                                  176  "             5'-chloro-3-hydroxy-                                                                         Red                                                            2',4'-dimethoxy-2-                                                            naphthanilide (Naph-                                                          tol AS-ITR)                                                177  "             3-methyl-1-(p-tolyl)-                                                                        Yellow                                                         5-hydroxypyrazole                                          178  "             3'-chloro-3-hydroxy-                                                                         Scarlet                                                        2-naphth-ortho-                                                               anisidide (Naphtol                                                            AS-NEL)                                                    179  4-aminomethyl-                                                                              3-hydroxy-2-napho-                                                                           Scarlet                                          aniline       ortho-toluidide                                                               (Naphtol AS-D)                                             180  "             4,4'-bi-ortho-aceto-                                                                         Greenish-                                                      acetotoluidide (Naph-                                                                        Yellow                                                         tol AS-G)                                                  181  "             3,3'"-diethoxy-4',                                                                           Yellow                                                         4'"-biacetoacet-                                                              anilide                                                    182  "             3-methyl-1-(p-tolyl)-                                                                        Yellow                                                         5-hydroxypyrazole                                          183  3-chloro-4-amino-                                                                           4'-chloro-3-hydroxy-                                                                         Scarlet                                          methylaniline 2-naphtho-ortho-                                                              toluidide (Naphtol                                                            AS-TR                                                      184  "             2',2'"-diodo-4',4'"-                                                                         Yellow                                                         biacetoacetanilide                                         185  "             3-methyl-1-(p-tolyl)-                                                                        Yellow                                                         5-hydroxypyrazole                                          186  "             4,4'-bi-ortho-aceto-                                                                         Yellow                                                         acetotoluidide (Naph-                                                         tol AS-G)                                                  187  3-ethoxy-4-amino-                                                                           3-hydroxy-2-naphtho-                                                                         Red                                              methylaniline 2,4-xylidide (Naph-                                                           tol AS-MX)                                                 188  "             3'-chloro-3-hydroxy-                                                                         Red                                                            2-naphth-ortho-                                                               anisidide                                                  189  "             2',2'"-dibromo-4',                                                                           Yellow                                                         4'"-biacetoacet-                                                              anilide                                                    190  "             3',3'"-diethoxy-4',                                                                          Yellow                                                         4'"-biacetoacet-                                                              anilide                                                    ______________________________________                                    

What is claimed is:
 1. A compound of the formula ##STR29## wherein: R ishydrogen, lower-alkyl, lower-alkoxy or halogen;R² is hydrogen,lower-alkyl, lower-alkoxy or halogen; and R¹ and R³ are aminomethyl. 2.A compound according to claim 1 wherein R is lower-alkoxy.
 3. A compoundaccording to claim 2 wherein R² is hydrogen.
 4. The compound accordingto claim 3 wherein R is methoxy.